EP0058813B1 - Elektrochrome Zelle mit einer aus einem zusammengesetzten Festkörper bestehenden, ionenleitenden Schicht - Google Patents

Elektrochrome Zelle mit einer aus einem zusammengesetzten Festkörper bestehenden, ionenleitenden Schicht Download PDF

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Publication number
EP0058813B1
EP0058813B1 EP82100007A EP82100007A EP0058813B1 EP 0058813 B1 EP0058813 B1 EP 0058813B1 EP 82100007 A EP82100007 A EP 82100007A EP 82100007 A EP82100007 A EP 82100007A EP 0058813 B1 EP0058813 B1 EP 0058813B1
Authority
EP
European Patent Office
Prior art keywords
sio
layer
electrochromic
codeposited
ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82100007A
Other languages
English (en)
French (fr)
Other versions
EP0058813A1 (de
Inventor
Robert Domenico Giglia
Gottfried Haacke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wyeth Holdings LLC
Original Assignee
American Cyanamid Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by American Cyanamid Co filed Critical American Cyanamid Co
Publication of EP0058813A1 publication Critical patent/EP0058813A1/de
Application granted granted Critical
Publication of EP0058813B1 publication Critical patent/EP0058813B1/de
Expired legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte

Definitions

  • the invention is an improvement in electrochromic devices having an electrochromic layer, such as a tungstic oxide film, in combination with a layer of inorganic ion-conductive insulating material.
  • the practical cycle life of the device is extended beyond the practical cycle life of devices that are made with a film of SiO used alone, or with a film made of Cr 2 O 3 alone.
  • the benefit of the addition of a small amount of Cr 2 O 3 to the SiO structure is believed to be derived from the fact that Cr 2 O 3 is more hygroscopic than SiO.
  • the mixture increases the water content of the insulating layer thereby resulting in an electronically insulating layer with improved protonic conduction.
  • the improved protonic conduction reduces the operating voltage of the device and thereby reduces the magnitude of the side reactions.
  • an electrochromic device comprising a layer of inorganic electrochromic material having one of its surfaces in ion-conductive contact with a surface of a single ion-conductive insulating layer which consists essentially of a codeposited mixture of SiO and Cr 2 O 3 , with those two layers disposed between two electrode surfaces with means for passing electric current in reversible directions through the two layers for alternate coloration and erasing of the electrochromic layer, characterized in that the mixture ratio of Cr 2 O 3 to SiO in said codeposited mixture is the equivalent of a ratio in the range from 2.5 to 50 nm film thickness of Cr 2 0 3 to 160 nm film thickness of SiO.
  • the electrochromic material used in the device is usually tungstic oxide but may also be any of the other inorganic compounds of transition metals that have the electrochromic property. A number of such inorganic electrochromic compounds have been described.
  • Devices embodying the invention may be made for any of a variety of uses such as electrochromic windows, lenses or mirrors in which the light transmission characteristics are modified by an electrochromic layer; or electrochromic display devices in which colored images such as a figure or a display of numbers or letters can be formed and erased in response to the application of electric current.
  • One display device of the latter kind is a digital display face for an electronic time piece such as a wristwatch.
  • Electrochromic numeric or alphanumeric displays can be used in electronic calculators and the like.
  • the electrodes and the substrate on which the functional layers are supported may be any of various suitable materials.
  • NESA glass, having a conductive tin oxide layer on a glass sheet is a convenient support and electrode combination which is often used to provide the supporting substrate and electrode on which an electrochromic layer is applied.
  • As a counter electrode any metallic or other electron-conductive material may be used. Coated gold or other metals are usually preferred.
  • a conductive layer of carbon paper can be used.
  • the supporting substrate we use a small sheet of glass having one surface covered by a conductive coated film of indium oxide, as obtained from Optical Coating Laboratory.
  • a film of electrochromic tungstic oxide, 100 mm thick, is coated by thermal deposition in vacuum over the indium oxide film surface.
  • a mixed film of mixed SiO and Cr 2 O 3 is deposited by simultaneous thermal deposition in vacuum.
  • the SiO and Cr 2 O 3 are evaporated separately but are codeposited as a single mixed film of both components.
  • the SiO and Cr 2 O 3 are simultaneously evaporated and deposited at relative rates and for a time that would separately deposit 160 nm SiO and 12 nm of Cr 2 O 3 , respectively.
  • an electrode layer of gold 12 nm thick is deposited by vacuum deposition. Terminal wires are connected to the indium oxide and gold electrodes and direct current pulses of opposite polarity are applied in turn to alternately color and erase the electrochromic layer of tungstic oxide. On each half cycle about 15 millicoulombs per square centimeter are passed. The device was continuously cycled in this mode at 20°C in air having 50% relative humidity.
  • the device passed 10,000 switching cycles with no sign of degradation in any of the layers.
  • Another device which had been constructed the same except with 5 nm of Cr 2 O 3 and 160 nm of SiO codeposited in the single ion-conductive layer, withstood the same test for better than 10,000 switching cycles.
  • a device made the same except with only Cr 2 O 3 in the ion conductive layer on cyclic testing will gradually build up a residual coloration in the Cr 2 O 3 layer which becomes quite noticeable after only one thousand switching cycles.
  • a codeposited layer containing about 160 nm of codeposited SiO for most devices.
  • the amount of SiO may range from about 80 to about 250 nm.
  • a most preferred ratio of the two components in the codeposited film is about 160 nm of SiO with from 2.5 to 5 nm of Cr 2 O 3 in the codeposited layer. Higher proportions of Cr 2 O 3 may be used, up to about 50 nm at which the inherent light absorption by the Cr 2 O 3 becomes noticeable.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Claims (3)

1. Elektrochrome Einrichtung mit einer Schicht eines anorganischen elektrochromen Materials, welche mit einer Oberfläche in lonen-leitenden Kontakt mit einer Oberfläche einer einzelnen lonen-leitenden isolierenden Schicht steht, welch letztere im wesentlichen aus einem gemeinsam abgeschiedenen Gemisch aus SiO und Cr2O3 besteht, wobei diese beiden Schichten zwischen zwei Elektrodenfläche angeordnet sind und wobei Einrichtungen vorgesehen sind, um einen elektrischen Strom mit umkehrbarer Richtung durch die beiden Schichten zu leiten zum Zwecke der alternierenden Färbung und Löschung der elektrochromen Schicht, dadurch gekennzeichnet, daß das Mischungsverhältnis von Cr2O3 zu SiO in der gemeinsam abgeschiedenen Schicht äquivalent ist einem Verhältnis einer Filmdicke von Cr2O3 von 2,5 bis 50 nm zu einer Filmdicke des SiO von 160 nm.
2. Elektrochrome Einrichtung nach Anspruch 1, dadurch gekennzeichnet, daß das elektrochrome Material ein elektrochromes Wolframoxid ist.
3. Elektrochrome Einrichtung nach Anspruch 1, dadurch gekennzeichnet, daß die Menge an SiO in der Schicht einer Filmdicke des SiO von etwa 160 nm äquivalent ist und daß die Menge des Cr2O3 in der gleichen Schicht einer Filmdicke des Cr2O3 von etwa 2,5 bis 5 nm äquivalent ist.
EP82100007A 1981-02-19 1982-01-04 Elektrochrome Zelle mit einer aus einem zusammengesetzten Festkörper bestehenden, ionenleitenden Schicht Expired EP0058813B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US235871 1981-02-19
US06/235,871 US4392721A (en) 1981-02-19 1981-02-19 Electrochromic cell having a mixed solid ion-conducting layer

Publications (2)

Publication Number Publication Date
EP0058813A1 EP0058813A1 (de) 1982-09-01
EP0058813B1 true EP0058813B1 (de) 1985-06-12

Family

ID=22887237

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82100007A Expired EP0058813B1 (de) 1981-02-19 1982-01-04 Elektrochrome Zelle mit einer aus einem zusammengesetzten Festkörper bestehenden, ionenleitenden Schicht

Country Status (5)

Country Link
US (1) US4392721A (de)
EP (1) EP0058813B1 (de)
JP (1) JPS57151916A (de)
CA (1) CA1169531A (de)
DE (1) DE3264091D1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58114020A (ja) * 1981-12-28 1983-07-07 Citizen Watch Co Ltd 全固体相補型エレクトロクロミツク表示素子の駆動方式
US5080471A (en) * 1990-04-06 1992-01-14 Eic Laboratories, Inc. Electrochromic material and electro-optical device using same
US5657150A (en) * 1993-09-10 1997-08-12 Eyeonics Corporation Electrochromic edge isolation-interconnect system, process, and device for its manufacture
GB9525740D0 (en) * 1995-12-15 1996-02-14 Klemantaski Sidney Apparatus for controlling movements of mollusca and the like
FR2746934B1 (fr) * 1996-03-27 1998-05-07 Saint Gobain Vitrage Dispositif electrochimique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5536860A (en) * 1978-09-06 1980-03-14 Fuji Photo Film Co Ltd Electrolytic coloring display device

Also Published As

Publication number Publication date
US4392721A (en) 1983-07-12
JPS57151916A (en) 1982-09-20
DE3264091D1 (en) 1985-07-18
EP0058813A1 (de) 1982-09-01
CA1169531A (en) 1984-06-19

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